Soil Nutrient Bioavailability—A Mechanistic Approach

Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are important sinks for trace elements in soil-residual systems. The pH of the soil-residual system is often the most important chemical property governing trace element sorption, precipitation, solubility, and availability. Trace element phytoavailability in residual-treated soils is often estimated using soil extraction methods. However, spectroscopic studies show that sequential extraction methods may not be accurate in perturbed soil-residual systems. Plant bioassay is the best method to measure the effect of residuals on phytoavailability. Key concepts used to describe phytoavailability are (i) the salt effect, (ii) the plateau effect, and (iii) the soil-plant barrier. Metal availability in soil from metal-salt addition is greater than availability in soil from addition of metal-containing residuals. Plant metal content displays plateaus at high residual loadings corresponding to the residual's metal concentration and sorption capacity. The soil-plant barrier limits transmission of many trace elements through the food chain, although Cd (an important human health concern) can bypass the soil-plant barrier. Results from many studies that support these key concepts provide a basis of our understanding of the relationship between trace element chemistry and phytoavailability in residual-treated soils. Research is needed to (i) determine mechanisms for trace element retention of soil-residual systems, (ii) determine the effect of residuals on ecological receptors and the ability of residuals to reduce ecotoxicity in metal-contaminated soil, and (iii) predict the long-term bioavailability of trace elements in soil-residual systems.

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Trace element chemistry in residual-treated soil: key concepts and metal bioavailability.

Trace Elements in Soils

The constant capacitance model, a chemical surface complexation model, was applied to arsenate, As(V), adsorption on 49 soils selected for variation in soil properties. The constant capacitance model was able to fit arsenate adsorption on all soils by optimizing either three monodentate or two bidentate As(V) surface complexation constants. A general regression model was developed for predicting soil As(V) surface complexation constants from easily measured soil chemical characteristics. These chemical properties were cation exchange capacity (CEC), inorganic C (IOC) content, organic C (OC) content, iron oxide content, and surface area (SA). The prediction equations were used to obtain values for the As(V) surface complexation constants for five additional soils, thereby providing a completely independent evaluation of the ability of the constant capacitance model to describe As(V) adsorption. The model's ability to predict As(V) adsorption was quantitative on three soils, semi-quantitative on one soil, and poor on another soil. Incorporation of these prediction equations into chemical speciation-transport models will allow simulation of soil solution As(V) concentrations under diverse agricultural and environmental conditions without the requirement of soil specific adsorption data and subsequent parameter optimization.

Predicting Boron Adsorption by Soils Using Soil Chemical Parameters in the Constant Capacitance Model

Assessment and field-scale mapping of soil quality properties of a saline-sodic soil

The USEPA standards (40 CFR Part 503) for the use or disposal of sewage sludge (biosolids) derived risk-based numerical values for Mo for the biosolids --> land --> plant --> animal pathway (Pathway 6). Following legal challenge, most Mo numerical standards were withdrawn, pending additional field-generated data using modern biosolids (Mo concentrations <75 mg kg(-1) and a reassessment of this pathway. This paper presents a reevaluation of biosolids Mo data, refinement of the risk assessment algorithms, and a reassessment of Mo-induced hypocuprosis from land application of biosolids. Forage Mo uptake coefficients (UC) are derived from field studies, many of which used modern biosolids applied to numerous soil types, with varying soil pH values, and supporting various crops. Typical cattle diet scenarios are used to calculate a diet-weighted UC value that realistically represents forage Mo exposure to cattle. Recent biosolids use data are employed to estimate the fraction of animal forage (FC) likely to be affected by biosolids applications nationally. Field data are used to estimate long-term Mo leaching and a leaching correction factor (LC) is used to adjust cumulative biosolids application limits. The modified UC and new FC and LC factors are used in a new algorithm to calculate biosolids Mo Pathway 6 risk. The resulting numerical standards for Mo are cumulative limit (RPc)=40 kg Mo ha(-1), and alternate pollutant limit (APL) = 40 mg Mo kg(-1) We regard the modifications to algorithms and parameters and calculations as conservative, and believe that the risk of Mo-induced hypocuprosis from biosolids Mo is small. Providing adequate Cu mineral supplements, standard procedure in proper herd management, would augment the conservatism of the new risk assessment.

Gary G. Van Riper

Papers

A modified risk assessment to establish molybdenum standards for land application of biosolids.